CN1187610C - Biosensor - Google Patents
Biosensor Download PDFInfo
- Publication number
- CN1187610C CN1187610C CNB018007341A CN01800734A CN1187610C CN 1187610 C CN1187610 C CN 1187610C CN B018007341 A CNB018007341 A CN B018007341A CN 01800734 A CN01800734 A CN 01800734A CN 1187610 C CN1187610 C CN 1187610C
- Authority
- CN
- China
- Prior art keywords
- sensor
- acid
- electrode
- reagent layer
- biology sensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 112
- 150000005846 sugar alcohols Chemical class 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 102000004190 Enzymes Human genes 0.000 claims description 31
- 108090000790 Enzymes Proteins 0.000 claims description 31
- 230000000694 effects Effects 0.000 claims description 29
- 239000000832 lactitol Substances 0.000 claims description 9
- 235000010448 lactitol Nutrition 0.000 claims description 9
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 claims description 9
- 229960003451 lactitol Drugs 0.000 claims description 9
- 239000000845 maltitol Substances 0.000 claims description 8
- 235000010449 maltitol Nutrition 0.000 claims description 8
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 claims description 7
- 229940035436 maltitol Drugs 0.000 claims description 7
- -1 organic acid salt Chemical class 0.000 abstract description 40
- 150000007524 organic acids Chemical class 0.000 abstract description 26
- 239000000126 substance Substances 0.000 abstract description 23
- 239000007788 liquid Substances 0.000 abstract description 21
- 230000004044 response Effects 0.000 abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 20
- 150000003839 salts Chemical class 0.000 abstract description 18
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000012488 sample solution Substances 0.000 description 36
- 229940088598 enzyme Drugs 0.000 description 30
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 24
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- 239000000463 material Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 13
- 230000000630 rising effect Effects 0.000 description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 12
- 239000008103 glucose Substances 0.000 description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 241001597008 Nomeidae Species 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 10
- 235000001014 amino acid Nutrition 0.000 description 9
- 229940024606 amino acid Drugs 0.000 description 9
- 150000001413 amino acids Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000008213 purified water Substances 0.000 description 8
- 230000036962 time dependent Effects 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 150000007933 aliphatic carboxylic acids Chemical group 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000006911 enzymatic reaction Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 5
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 5
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000002837 carbocyclic group Chemical group 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 229940093915 gynecological organic acid Drugs 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 229960003080 taurine Drugs 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 108010015776 Glucose oxidase Proteins 0.000 description 4
- 239000004366 Glucose oxidase Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 4
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 4
- 239000004472 Lysine Substances 0.000 description 4
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000013098 chemical test method Methods 0.000 description 4
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- 229940116332 glucose oxidase Drugs 0.000 description 4
- 235000019420 glucose oxidase Nutrition 0.000 description 4
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000004043 responsiveness Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 3
- 239000004473 Threonine Substances 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 239000001175 calcium sulphate Substances 0.000 description 3
- 235000011132 calcium sulphate Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 108010050375 Glucose 1-Dehydrogenase Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- HSNZZMHEPUFJNZ-UHFFFAOYSA-N L-galacto-2-Heptulose Natural products OCC(O)C(O)C(O)C(O)C(=O)CO HSNZZMHEPUFJNZ-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
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- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
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- 239000011668 ascorbic acid Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 2
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 2
- 210000000601 blood cell Anatomy 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
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- 150000007942 carboxylates Chemical class 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 239000010931 gold Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
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- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 2
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 229960005137 succinic acid Drugs 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
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- GMLLYEDWRJDBIT-UHFFFAOYSA-J magnesium;dipotassium;disulfate Chemical compound [Mg+2].[K+].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GMLLYEDWRJDBIT-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
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- 229960001855 mannitol Drugs 0.000 description 1
- 150000002699 mannoheptose derivatives Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- OJSWEKSDNUORPG-UHFFFAOYSA-H neodymium(3+);trisulfate Chemical compound [Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OJSWEKSDNUORPG-UHFFFAOYSA-H 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- SJQCGMLIMSXKBO-UHFFFAOYSA-K potassium cobalt(2+) trinitrite Chemical compound [K+].[Co++].[O-]N=O.[O-]N=O.[O-]N=O SJQCGMLIMSXKBO-UHFFFAOYSA-K 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- HSNZZMHEPUFJNZ-SHUUEZRQSA-N sedoheptulose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO HSNZZMHEPUFJNZ-SHUUEZRQSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 1
- 229940119523 thallium sulfate Drugs 0.000 description 1
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 1
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 1
- 229910000384 uranyl sulfate Inorganic materials 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/001—Enzyme electrodes
- C12Q1/002—Electrode membranes
- C12Q1/003—Functionalisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Biotechnology (AREA)
- Biophysics (AREA)
- Analytical Chemistry (AREA)
- Immunology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
In a biosensor for measuring a specific substance in a liquid sample, one or a combination of sugar alcohol, metallic salt, organic acid or organic acid salt which has at least one carboxyl group in a molecule, and organic acid or organic acid salt which has at least one carboxyl group and one amino group in a molecule, is included in a reagent layer provided on electrodes, thereby providing a highly-accurate biosensor which is excellent in stability and has high response (sensitivity, linearity) of the sensor to the substrate concentration.
Description
Technical field
The present invention relates to analyze the biology sensor of the specific composition in the liquor sample, particularly constitute biology sensor reagent layer reagent constitute.
Background technology
Biology sensor is the molecule distinguishability that utilizes biomaterials such as microorganism, enzyme, antibody, with the sensor of biomaterial as molecular recognition elements.That is, the biomaterial that is immobilized is when the recognition objective predetermined substance, the consumption of the oxygen that utilize the reaction cause, is caused by the breathing of microorganism, enzyme reaction, luminous etc. material.
In biology sensor, the practicability of enzyme sensor is progressive, and the enzyme sensor of using as glucose, lactic acid, cholesterol, lactose, urea, amino acid just is being applied to medical treatment detection or food industry.The electronics that the matrix that contains in the test liquid of enzyme sensor utilization as a corpse or other object for laboratory examination and chemical testing and the reaction of enzyme generate reduces electron acceptor, and determinator utilizes the also commercial weight of this electron acceptor of electrochemical method instrumentation, carries out the quantitative test of a corpse or other object for laboratory examination and chemical testing.As one of this class biology sensor example, known have the spy to be willing to the sensor that proposes in flat 11-324511 number.
Figure 11, the 12nd, the exploded perspective view of the biology sensor that existing blood-sugar level measuring is used.On insulated type substrates such as polyethylene terephthalate 1,101, form the mensuration electrode 2,102 (being also referred to as the effect utmost point) formed by conductive material, to electrode 3,103 (being also referred to as) and detecting electrode 4 to the utmost point, on these electrodes formation contain with test liquid in enzyme, electron transit mediator, the reagent layer 5,105 of hydrophilic macromolecule of special component specific reaction.
For forming the cavity that detects the current value that generates by the reagent reacting in special component in the test liquid and the reagent layer 5,105 with above-mentioned electrode 2,3,4,102,103, be fitted in the cover plate 8,108 that part place on electrode and the reagent layer has the dividing plate 6,106 of elongated cuts portion 7,107 and formed airport 9,109 on the insulated substrate.
In the biology sensor that so constitutes, test liquid utilizes capillarity to supply with in cavity from the inlet (test liquid attracts mouth) of cavity, guides to certain position of electrode and reagent layer.The special component in the test liquid and the reagent reacting of reagent layer generate electric current, and the electric current of generation obtains existing outside determinator by biology sensor and reads, and carries out the quantitative test of a corpse or other object for laboratory examination and chemical testing.
But, in the biology sensor that above-mentioned reagent constitutes, in the presence of heat or moisture, particularly in temperature more than 30 ℃, under the many wet environments of the high temperature of humidity more than 80%, be contained in zymoprotein in the reagent layer 5,105 or part of hydrophilic macromolecule etc. and electron transit mediator generation reduction reaction, so produce background current (noise current), background current value time dependent ground rises, the problem that exists sensor performance significantly to worsen.
As the means that address this problem, preserve in the container at the biology sensor of the container molding that uses alumiseal or resin etc., enclose drying agent such as silica gel or activated alumina, be used for removing moisture, preventing the mis-behave of sensor, is can't remove fully to be included in the biology sensor water of remaining molecular level in the reagent but utilize this class drying agent merely.
Even in above-mentioned preservation container, after the long time, be difficult to also accomplish that moisture invades not at all, the reduction reaction of the part of electron transit mediator and zymoprotein and hydrophilic macromolecule, only in the presence of the moisture of denier, just can carry out, so the extremely difficult time dependent that suppresses background current rises, this is the problem of its existence.
When containing inorganic salts such as the potassium ferricyanide in the mix reagent layer of forming by all ingredients such as enzyme or electron transit mediators, in the dry run of reagent solution, reagent layer is very easy to crystallization, the rough surface of reagent layer, become uneven state, cause responsiveness (rectilinearity, sensitivity) or measure deterioration such as precision with respect to the substrate concentration of sensor.
The present invention is for addressing the above problem, purpose is to provide a kind of and is effectively preventing because of when contacting the performance degradation that causes biology sensor with moisture, with respect to the high high-precision biology sensor of responsiveness (rectilinearity or sensitivity) of the substrate concentration of sensor.
Disclosure of an invention
The biology sensor of first invention of the present invention, it is the biology sensor of measuring the concentration of the predetermined substance in the sample solution, it is characterized in that, for being dissolved in the sample solution and reacting specifically with predetermined substance in the sample solution, and in the reagent layer that sets in advance, contain sugar alcohol, do not hinder enzyme reaction etc., can suppress the rising of background current by the time, also can suppress simultaneously with blood in the unnecessary reactions of the various altogether miscellaneous materials that exist, rectilinearity is good, and (slope of regression equation is big, intercept is little), and the deviation between each sensor is little.
The biology sensor of second invention of the present invention, it is the sensor of above-mentioned the 1st invention, be characterised in that, use be arranged on the insulativity substrate at least by the concentration of the effect utmost point and the above-mentioned predetermined substance of determination of electrode that the utmost point is formed, be a kind of biology sensor of utilizing electrode to check of being suitable for.
The sensor of the 3rd invention of the present invention, it is the sensor of above-mentioned second invention, it is characterized in that, the mentioned reagent layer is formed on the above-mentioned electrode, perhaps the reagent at this reagent layer is dissolved in configured electrodes in the diffusion region that diffuses to form in the test liquid, at least containing enzyme and electron transit mediator in this reagent layer, is the biology sensor that a kind of reaction that is fit to utilize enzyme and electron transit mediator is checked.
The biology sensor of the 4th invention of the present invention, it is the biology sensor of each invention among the above-mentioned 1-3, it is characterized in that, above-mentioned sugar alcohol is the chain polyvalent alcohol, or ring type sugar alcohol, or their replacement body or derivant, be the invention that first sugar alcohol in the invention specialized, can obtain same effect with first invention.
The biology sensor of the 5th invention of the present invention, it is each sensor in the above-mentioned 1-3 item, wherein said sugar alcohol is a kind of in maltitol, the lactitol or two kinds, is the invention that first sugar alcohol in the invention specialized, and can obtain same effect with first invention.
The biology sensor of the 6th invention of the present invention, it is the biology sensor of measuring the concentration of the predetermined substance in the sample solution, it is characterized in that, for being dissolved in the sample solution and reacting specifically with predetermined substance in the sample solution, and in the reagent layer that sets in advance, contain slaine, do not hinder enzyme reaction etc., can suppress the rising of background current by the time.
The biology sensor of the 7th invention of the present invention, it is the sensor of above-mentioned the 6th invention, be characterised in that, use be arranged on the insulativity substrate at least by the concentration of the effect utmost point and the above-mentioned predetermined substance of determination of electrode that the utmost point is formed, be a kind of biology sensor of utilizing electrode to check of being suitable for.
The sensor of the 8th invention of the present invention, it is the sensor of above-mentioned the 7th invention, it is characterized in that, the mentioned reagent layer is formed on the above-mentioned electrode, perhaps the reagent at this reagent layer is dissolved in configured electrodes in the diffusion region that diffuses to form in the test liquid, at least containing enzyme and electron transit mediator in this reagent layer, is the biology sensor that a kind of reaction that is fit to utilize enzyme and electron transit mediator is checked.
The biology sensor of nine inventions of the present invention, it is the biology sensor of each invention among the above-mentioned 6-8, it is characterized in that, above-mentioned slaine is sulfuric acid slaine, hydrogen sulfate slaine, sulfurous acid metal salt, bisulfite slaine, the hydrosulfurous acid slaine, be the invention that the 6th slaine in the invention specialized, can obtain same effect with the 6th invention.
The biology sensor of the of the present invention ten invention, it is each sensor in the above-mentioned 6-8 item, wherein said slaine is a kind of in magnesium sulphate, the calcium sulphate or two kinds, is the invention that the 6th slaine in the invention specialized, and can obtain same effect with the 6th invention.
The biology sensor of the 11 invention of the present invention, it is each sensor in the above-mentioned 6-8 item, wherein said slaine is nitric acid slaine, nitric acid hydrogen slaine, nitrous acid slaine, nitrous acid hydrogen slaine or inferior nitrous acid slaine, be the invention that the 6th slaine in the invention specialized, can obtain same effect with the 6th invention.
The biology sensor of the tenth binomial invention of the present invention, it is each sensor in the above-mentioned 6-8 item, wherein said slaine is a kind of in magnesium nitrate, the calcium nitrate or two kinds, is the invention that the 6th slaine in the invention specialized, and can obtain same effect with the 6th invention.
The biology sensor of the 13 invention of the present invention, it is the biology sensor of measuring the concentration of the predetermined substance in the sample solution, it is characterized in that, for being dissolved in the sample solution and reacting specifically with predetermined substance in the sample solution, and in the reagent layer that sets in advance, contain organic acid or the acylate that at least one carboxyl is arranged in the molecule, do not hinder enzyme reaction etc., can suppress the rising of background current by the time, also can suppress simultaneously with blood in the unnecessary reactions of the various altogether miscellaneous materials that exist, rectilinearity is good, and (slope of regression equation is big, intercept is little), and the deviation between each sensor is little.
The biology sensor of the 14 invention of the present invention, it is the sensor of above-mentioned the 13 invention, be characterised in that, use be arranged on the insulativity substrate at least by the concentration of the effect utmost point and the above-mentioned predetermined substance of determination of electrode that the utmost point is formed, be a kind of biology sensor of utilizing electrode to check of being suitable for.
The sensor of the 15 invention of the present invention, it is the sensor of above-mentioned the 13 invention, it is characterized in that, the mentioned reagent layer is formed on the above-mentioned electrode, perhaps the reagent at this reagent layer is dissolved in configured electrodes in the diffusion region that diffuses to form in the test liquid, at least containing enzyme and electron transit mediator in this reagent layer, is the biology sensor that a kind of reaction that is fit to utilize enzyme and electron transit mediator is checked.
The biology sensor of the 16 invention of the present invention, it is the biology sensor of each invention among the above-mentioned 13-15, it is characterized in that, above-mentioned organic acid is aliphatic carboxylic acid, carbocyclic ring carboxylic acid, heterocyclic carboxylic acid or their replacement body or derivant, be the invention that the 13 organic acid in the invention specialized, can obtain same effect with the 13 invention.
The biology sensor of the 17 invention of the present invention, it is each sensor in the above-mentioned 13-15 item, wherein said organic acid is one or two or more kinds the combination in glutaric acid, hexane diacid, phthalic acid, the benzoic acid, be the invention that the 13 carboxylic acid in the invention specialized, can obtain same effect with the 13 invention.
The biology sensor of the 18 invention of the present invention, it is the biology sensor of measuring the concentration of the predetermined substance in the sample solution, it is characterized in that, for being dissolved in the sample solution and reacting specifically with predetermined substance in the sample solution, and in the reagent layer that sets in advance, contain at least one carboxyl and amino organic acid or acylate are arranged in the molecule, because can be fine and close and form reagent layer in heterogeneity, so raising that can be tremendous is with respect to the responsiveness of substrate concentration (sensitivity, value linear).
The biology sensor of the 19 invention of the present invention, it is the sensor of above-mentioned the 18 invention, be characterised in that, use be arranged on the insulativity substrate at least by the concentration of the effect utmost point and the above-mentioned predetermined substance of determination of electrode that the utmost point is formed, be a kind of biology sensor of utilizing electrode to check of being suitable for.
The sensor of the 20 invention of the present invention, it is the sensor of above-mentioned the 19 invention, it is characterized in that, the mentioned reagent layer is formed on the above-mentioned electrode, perhaps the reagent at this reagent layer is dissolved in configured electrodes in the diffusion region that diffuses to form in the test liquid, at least containing enzyme and electron transit mediator in this reagent layer, is the biology sensor that a kind of reaction that is fit to utilize enzyme and electron transit mediator is checked.
The biology sensor of the 21 invention of the present invention, it is the biology sensor of each invention among the above-mentioned 18-20, it is characterized in that, above-mentioned organic acid is amino acid or its replacement body or derivant, be the invention that the 18 organic acid in the invention specialized, can obtain same effect with the 18 invention.
The biology sensor of the 20 binomial invention of the present invention; it is each sensor in the above-mentioned 18-20 item; wherein said amino acid is one or two or more kinds the combination in glycocoll, serine, proline, threonine, lysine, the taurine; be the invention that the 18 carboxylic acid in the invention specialized, can obtain same effect with the 18 invention.
The biology sensor of the 23 invention of the present invention, it is the biology sensor of measuring the concentration of the predetermined substance in the sample solution, it is characterized in that, for being dissolved in the sample solution and reacting specifically with predetermined substance in the sample solution, and in the reagent layer that sets in advance, contain sugar alcohol, slaine, have in the molecule at least one carboxyl and amino organic acid or the two or more at least combination in the acylate are arranged in the organic acid of at least one carboxyl or acylate or the molecule, good stability, and responsiveness (sensitivity with respect to substrate concentration, value is linear) height is a kind of high-precision sensor.
The biology sensor of 24 inventions of the present invention, it is the sensor of above-mentioned 1-23 item invention, it is characterized in that, in above-mentioned reagent layer, also contain hydrophilic macromolecule, so because contain hydrophilic macromolecule forms homogeneous easily at electrode surface reagent, the effect of the closed state of can be improved electrode and reagent.In addition,, form, can provide the deviation between each sensor few high-performance biology sensor so can realize the reagent of homogeneous because each material becomes the state that homogeneous disperses in reagent layer.
The simple declaration of accompanying drawing
Fig. 1 is illustrated in the sensor response characteristics when adding lactitol as sugar alcohol among the embodiment 1 in sample solution.
Fig. 2 is illustrated in the sensor response characteristics when adding maltitol as sugar alcohol among the embodiment 1 in sample solution.
Fig. 3 is illustrated among the embodiment 1 rising of the background current under the cruel environment of mistake when using Purified Water as sample solution.
Fig. 4 is illustrated among the embodiment 1 rising of the whole blood response value under the cruel environment of mistake when using whole blood as sample solution.
Fig. 5 is illustrated among the embodiment 2 rising of the background current under the cruel environment of mistake when using Purified Water as sample solution.
Fig. 6 is illustrated among the embodiment 2 rising of the whole blood response value under the cruel environment of mistake when using whole blood as sample solution.
Fig. 7 is illustrated among the embodiment 3 rising of the background current under the cruel environment of mistake when using Purified Water as sample solution.
Fig. 8 is illustrated among the embodiment 4 rising of the background current under the cruel environment of mistake when using Purified Water as sample solution.
Fig. 9 is illustrated in the whole blood response value when using whole blood as sample solution among the embodiment 5.
Figure 10 is illustrated in the whole blood response value when using whole blood as sample solution among the embodiment 5.
Figure 11 is one of the exploded perspective view example of the biology sensor of 3 electrode modes.
Figure 12 is one of the exploded perspective view example of the biology sensor of 2 electrode modes.
The preferred plan that carries out an invention
The biology sensor of embodiment of the present invention 1 below is described.Should illustrate, in each embodiment of the present invention of following explanation, use enzyme as with sample solution in the molecular recognition elements of predetermined substance specific reaction, be that example describes with this enzyme sensor.
Figure 11 is one of the exploded perspective view example of the biology sensor of 3 electrode modes, and Figure 12 is one of the exploded perspective view example of the biology sensor of 2 electrode modes.Among Figure 11 and Figure 12,1,101 is the insulativity substrate, on this insulativity substrate 1,101 according to the rules position and shape form the mensuration electrode 2,102 that forms by conductive material, to electrode 3,103.In the biology sensor of 3 electrode modes shown in Figure 11, also in accordance with regulations position and shape is formed with and detects electrode 4 on the substrate 1 of insulativity.The said electrode 4 that detects has the function that detects corpse or other object for laboratory examination and chemical testing quantity not sufficient, can be used as contrast electrode or the part of electrode is used.
Material as the above-mentioned insulativity substrate 1,101 that is fit to has polyethylene terephthalate, polycarbonate, polyimide etc.
Constitute the conductive material of each electrode, monomer materials such as noble metals such as gold, platinum, palladium or graphite are for example arranged, or compound substances such as carbon paste or noble metal paste.
Monomer materials such as noble metals such as gold, platinum, palladium or carbon paste, can utilize splash vapour deposition method etc. easily to form conductive layer on insulativity substrate 1,101, compound substances such as carbon paste or noble metal paste can utilize methods such as serigraphy to form conductive layer on insulativity substrate 1,101.
When forming each electrode, utilize above-mentioned splash vapour deposition method or silk screen print method etc. on insulativity substrate 1,101, to form all sidedly, perhaps after forming above-mentioned conductive layer on the part, utilize laser etc. that slit is set, cut apart the formation electrode thus.In addition, use the silk screen print method of the galley be pre-formed electrode pattern or mask or splash vapour deposition method etc., also can form electrode equally.
On the electrode of above-mentioned formation, form the reagent layer 5,105 that contains enzyme, electron transit mediator, hydrophilic macromolecule and sugar alcohol.
Embodiment of the present invention 1 are characterised in that, contain sugar alcohol in reagent layer 5,105.In the reagent layer 5,105 that on electrode, forms, a part of functional group that the reactivity that exists in zymoprotein that contains in the electron transit mediator of this sugar alcohol and oxidized form, the reagent and the hydrophilic macromolecule etc. is abundant etc. contacts, and has the electron transit mediator of inhibition and is changed into the function of reduced form (being reduced) by oxidized form.
Therefore, in the biology sensor that mentioned reagent constitutes, in the presence of heat or moisture, particularly temperature is more than 30 ℃, under the how warm environment of the high temperature of humidity more than 80%, the background current (noise current) that the time dependent that the reduction reaction of the zymoprotein that contains in the reagent layer 5,105 or the part of hydrophilic macromolecule etc. and electron transit mediator causes rises can be suppressed, and can prevent the mis-behave of biology sensor.
By in reagent layer, containing sugar alcohol, can suppress with blood in the various unnecessary reactions of miscellaneous materials altogether that particularly exist in the blood cell, rectilinearity good (slope of regression equation is big, and intercept is little), and the deviation between each sensor is few, and high performance biology sensor can be provided.
As the above-mentioned sugar alcohol that contains in the reagent layer 5,105, the polyvalent alcohol or the ring type sugar alcohol of chains such as D-sorbite, maltitol, xylitol, mannitol, lactitol, reduction パ ラ チ ノ one ス, arabitol, glycerine, ribitol, galactitol, sedoheptose alcohol, mannoheptose, sedoheptulose, styracitole, polygalite, iditol, talitol, Allit, イ シ リ ト one Le, reduction starch saccharification thing for example arranged.
The steric isomer of these sugar alcohols, replacement body or derivant also can obtain same effect.
In these sugar alcohols, maltitol and lactitol can be described as and suppress above-mentioned background electric current effect best material because the bill of materials price ratio more cheaply and easily obtains.
The addition of these sugar alcohols is 0.1-500mM as sample solution concentration, preferred 1-100mM.
Biology sensor shown in Figure 11 and 12, afterwards, fitting on the reagent layer 5,105 that so forms, electrode 2,3,4,102,103 has the dividing plate 6,106 and the cover plate 8,108 of notch 7,107, forms the cavity of supplying with test liquid.
The suitable material of aforementioned barriers 6,106 and cover plate 8,108 for example has polyethylene terephthalate, polycarbonate, polyimide, polybutylene terephthalate, polyamide, Polyvinylchloride, Vingon, nylon etc.
Utilize capillarity to realize supplying with sample solution,, also be necessary to have airport 9,109 in the cavity, so that air is discharged to the outside of biology sensor except realizing supplying with reposefully the sample solution to the biology sensor that constitutes by above-mentioned cavity.
The configuration of airport 9,109 as long as in the scope that does not hinder test liquid to supply with, can be positioned at any position of cavity.
In the biology sensor of above-mentioned formation, the current value that special component in the test liquid and reagent layer 5,105 reactions that contain enzyme etc. obtain, by measure electrode 2,102, to electrode 3,103, detect the wire portion separately 10,11,12,110,111 of electrode 4, read by the determinator of the outside that connects.
The biology sensor of embodiment of the present invention 2 below is described.
The biology sensor of embodiment of the present invention 2, shown in Figure 11 and 12, reagent layer 5,105 is formed by enzyme, electron transit mediator, hydrophilic macromolecule and slaine.Other inscape is identical with aforesaid embodiment 1, so omit explanation.
Embodiment of the present invention 2, be characterised in that in reagent layer 5,105 and contain slaine, this slaine can be suppressed in the reagent layer 5,105 that forms on the electrode, the zymoprotein that contains in oxidized form electron transit mediator and the reagent and be present in that the abundant a part of functional group of reactivity in the hydrophilic macromolecule etc. contacts and the electron transit mediator that causes by the modification (be reduced) of oxidized form to reduced form.
Therefore in the biology sensor that mentioned reagent constitutes, in the presence of heat or moisture, particularly temperature is more than 30 ℃, under the many wet environments of the high temperature of humidity more than 80%, the background current (noise current) that the time dependent that the reduction reaction of the zymoprotein that contains in the reagent layer 5,105 or the part of hydrophilic macromolecule etc. and electron transit mediator causes rises can be suppressed, and can prevent the mis-behave of biology sensor.
As reagent layer 5, the slaine that contains in 105, sulfuric acid slaine or nitric acid slaine etc. are effective especially, the sulfuric acid slaine is for example arranged, the hydrogen sulfate slaine, sulfurous acid metal salt, the bisulfite slaine, or hydrosulfurous acid slaine, be specially aluminium sulphate, magnesium sulphate, zinc sulfate, antimony sulfate, indium sulfate, uranyl sulfate, uranous sulfate, cadmium sulfate, glazier's salt, gallium sulfate, calcium sulphate, silver sulfate, chromium sulfate, cobaltous sulphate, potassium acid sulfate, zirconium sulfate, mercuric sulfate, STANNOUS SULPHATE CRYSTALLINE, strontium sulfate, cesium sulfate, cerous sulfate, thallium sulfate, titanium sulfate, iron sulfate, copper sulphate, sodium sulphate, lead sulfate, nickelous sulfate, Dineodymium trisulfate, vanadic sulfate, palladium sulfate, barium sulphate, bismuth sulfate, praseodymium sulfate, beryllium sulfate, manganese sulfate, lanthanum sulfate, lithium sulfate, rubidium sulfate, aluminium potassium sulfate, aluminum sodium sulfate, uranyl potassium sulfate, chromium potassium suplhate, the sulfuric acid disodium magnesium, the magnesium sulphate dipotassium, the manganese sulfate caesium, rubidium sulfate aluminium, potassium acid sulfate, niter cake, potassium sulfite, calcium sulfite, sodium sulphite, barium sulfite, the sulphurous acid bismuth, sodium hydrosulfite, potassium bisulfite, sodium bisulfite etc., as the nitric acid slaine, nitric acid hydrogen slaine, nitrous acid hydrogen slaine or inferior nitrous acid slaine have aluminium nitrate, magnesium nitrate, zinc nitrate, nitric acid antimony, ytterbium nitrate, yttrium nitrate, indium nitrate, uranyl nitrate, erbium nitrate, cadmium nitrate, gadolinium nitrate, potassium nitrate, calcium nitrate, silver nitrate, chromic nitrate, cobalt nitrate, samaric nitrate, zirconium nitrate, dysprosium nitrate, mercuric nitrate, nitric acid tin, strontium nitrate, cesium nitrate, cerous nitrate, thallium nitrate, ferric nitrate, terbium nitrate, copper nitrate, thorium nitrate, sodium nitrate, plumbi nitras, nickel nitrate, neodymium nitrate, palladium nitrate, barium nitrate, bismuth nitrate, praseodymium nitrate, beryllium nitrate, holmium nitrate, manganese nitrate, europium nitrate, lanthanum nitrate, lithium nitrate, the nitric acid ruthenium, rubidium nitrate, rhodium nitrate, thallium nitrate mercury, potassium nitrite, silver nitrite, calcium nitrite, sodium nitrite, cobalt potassium nitrite, natrium cobaltinitrosum, inferior sodium nitrite etc.
In these slaines, particularly the moisture absorption of magnesium sulphate, calcium sulphate, magnesium nitrate, calcium nitrate prevents the effect height, so preferred.
The addition of slaine is 0.1-500mM, more preferably 1-50mM as reagent solution concentration.
The biology sensor of embodiment of the present invention 3 below is described.
The biology sensor of embodiment of the present invention 3, shown in Figure 11 and 12, reagent layer 5,105 is by having the organic acid of at least one carboxyl or acylate to form in enzyme, electron transit mediator, hydrophilic macromolecule and the molecule.Other inscape is identical with aforesaid embodiment 1, so omit explanation.
Embodiment of the present invention 3, be characterised in that and in reagent layer 5,105, contain organic acid or the acylate that at least one carboxyl is arranged in the molecule, have the organic acid of at least one carboxyl or acylate can be suppressed at the zymoprotein that contains in the oxidized form electron transit mediator and reagent in the reagent layer 5,105 that forms on the electrode in this molecule and be present in that the abundant a part of functional group of reactivity in the hydrophilic macromolecule etc. contacts and the electron transit mediator that causes by the modification (be reduced) of oxidized form to reduced form.
Therefore in the biology sensor that mentioned reagent constitutes, in the presence of heat or moisture, particularly temperature is more than 30 ℃, under the many wet environments of the high temperature of humidity more than 80%, the background current (noise current) that the time dependent that the reduction reaction of the zymoprotein that contains in the reagent layer 5,105 or the part of hydrophilic macromolecule etc. and electron transit mediator causes rises can be suppressed, and can prevent the mis-behave of biology sensor.
By in reagent layer, containing organic acid or the acylate that at least one carboxyl is arranged in the molecule, can suppress with blood in the various unnecessary reactions of miscellaneous materials altogether that particularly exist in the blood cell, rectilinearity is good, and (slope of regression equation is big, intercept is little), and the deviation between each sensor is few, and high performance biology sensor can be provided.
Organic acid or acylate as at least one carboxyl is arranged in the molecule that contains in the reagent layer 5,105 have aliphatic carboxylic acid, carbocyclic ring carboxylic acid, heterocyclic carboxylic acid etc., and salt.
For example, as aliphatic carboxylic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, maleic acid, fumaric acid etc. and salt thereof are arranged.
Straight chain is long more, molecular weight is big more, and effect is good more, preferably has the material of 3 above hydrocarbon chains especially.The reagent requirement that is used for biology sensor wants high to the dissolubility of water, so preferably have a plurality of hydrophilic functional groups in the molecular configuration.
As the carbocyclic ring carboxylic acid, benzoic acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA) etc. or its salt are arranged, use these materials also can obtain the effect identical with above-mentioned substance.
As heterocyclic carboxylic acid, the acid of 2-Off Le, nicotinic acid, isonicotinic acid etc. or its salt are for example arranged, use these materials also can obtain the effect identical with above-mentioned substance.
Above-mentioned aliphatics and carbocyclic ring carboxylic acid, have beyond the carboxylic acid or carboxylate of heterocycle, a part of functional group of carboxylic acid and carboxylate also can be obtained the effect identical with above-mentioned substance by what other functional group replaced as malic acid, ethane diacid one ethyl acetoacetic acid, citric acid, ketoglutaric acid etc. or its salt.
Optimal material is glutaric acid, hexane diacid, phthalic acid, benzoic acid in these organic acids or the acylate.
The addition of these organic acids or acylate is as reagent solution concentration, in the 0.01-100mM scope, preferably in the 0.1-10mM scope.
The biology sensor of embodiment of the present invention 4 below is described.
The biology sensor of embodiment of the present invention 4, shown in Figure 11 and 12, reagent layer 5,105 is by having at least one carboxyl and amino organic acid or acylate to form in enzyme, electron transit mediator, hydrophilic macromolecule and the molecule.Other inscape is identical with aforesaid embodiment 1, so omit explanation.
Embodiment of the present invention 4, be characterised in that in reagent layer 5,105, to contain at least one carboxyl and amino organic acid or acylate are arranged in the molecule, by in reagent layer 5,105, adding this organic acid or acylate, can make the surface state of reagent layer 5,105 very level and smooth, and can form in heterogeneity.When particularly in reagent layer 5,105, containing the inorganic salts such as the potassium ferricyanide that use as electron transit mediator, the easy crystallization of reagent layer in the dry run in the reagent solution, but by in reagent, containing at least one carboxyl and amino organic acid or acylate are arranged in the molecule, can suppress the crystallization of these inorganic salts.
The repressed inorganic salts of crystallization exist in reagent layer with small particle state, thus can with the enzyme molecule closely, contact equably, realize the good reagent layer state of electron transport efficient with the enzyme molecule.
Because can improve the dissolubility of reagent layer, so the sensitivity of sensor and rectilinearity can improve tremendously.
As at least one carboxyl and amino organic acid or acylate are arranged in the molecule that contains in the reagent layer 5,105; glycocoll, alanine, valine, leucine, isoleucine, serine, threonine, methionine, aspartic acid, glutamic acid, arginine, lysine, histidine, phenylalanine, tryptophane, proline etc. or its salt are for example arranged, or organic acid or acylate such as methyl amimoacetic acid, betaine, taurine.
The replacement body or the derivant of these organic acids or acylate also can obtain same effect.
In these organic acids or acylate, glycocoll, serine, proline, methionine, lysine, taurine have the effect of extra high inhibition crystallization, so preferred.
The addition of these organic acids or acylate is in the 0.1-1000mM scope as reagent solution concentration, preferably in the 10-500mM scope.
Embodiment of the present invention 1-4, for example understanding respectively has at least one carboxyl and the amino organic acid or the example of acylate in organic acid that at least one carboxyl is arranged or acylate, the molecule in mentioned reagent layer 5,105 adds sugar alcohols, slaine, molecule, these schemes also can applied in any combination.
The enzyme that contains in the reagent of above-mentioned embodiment 1-4, glucose oxidase, lactate oxidase, cholesterol oxidase, cholesterol esterase, uricase, ascorbic acid oxidase, bilirubin oxidase, glucose dehydrogenase, lactate dehydrogenasa etc. are for example arranged, as electron transit mediator, the potassium ferricyanide, 1,4-benzoquinone and its derivant, phenazine methosulfate, methyl blue, ferrocene and its derivant etc. are arranged.
Among embodiment of the present invention 1-4, be illustrated for the hydrophilic macromolecule that contains in the reagent layer 5,105, by in reagent layer 5,105, containing hydrophilic macromolecule, can make reagent solution have viscosity, on electrode, form reagent easily in heterogeneity, can improve the adaptation between electrode and the reagent simultaneously.By containing hydrophilic macromolecule, the dried reagent crystalline state of reagent homogeneous can also be made in addition, high-precision biology sensor can be prepared.
The hydrophilic macromolecule that is used for above purpose for example has polyaminoacid and its salt, polystyrolsulfon acid, gelatin and its derivant, acrylic acid and its salt, methacrylic acid and its salt, starch and its derivant, maleic anhydride and its salt, Ago-Gel and its derivants etc. such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, ethyl cellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polylysine.
Among embodiment of the present invention 1-4, illustrated that above-mentioned reagent layer is arranged on the electrode, particularly, configuration reagent layer 5,105 on the integral body of electrode or a part, in addition, in the scope of the mis-behave that does not make biology sensor, promptly, reagent in the reagent layer is dissolved in the diffusion region of spreading in the test liquid electrode is set, configuration reagent layer 5,105.
On the insulated substrate of making by polyethylene terephthalate, utilize the splash evaporation to form the thick palladium membranes of about 10nm on the whole on the surface of insulated substrate, utilize YAG laser on the part of above-mentioned film, to form slit afterwards, with dividing electrodes form to measure electrode, to electrode with detect electrode.Drip the aqueous solution that contains enzyme (glucose oxidase), electron transit mediator (potassium ferricyanide), hydrophilic macromolecule (carboxymethyl cellulose) and sugar alcohol with circle thereon, to measure electrode is the center, covering is to an electrode and a part that detects electrode, and drying forms reagent layer.The dividing plate with otch and the same cover plate that forms by polyethylene terephthalate of fitting thereon again and forming by polyethylene terephthalate with airport, formation becomes the cavity capillaceous that imports blood, makes the blood-sugar level measuring sensor of 3 electrode modes.
Sensor response characteristics when Fig. 1 is illustrated in the reagent solution and adds lactitol as sugar alcohol, test liquid is a whole blood, changes the concentration of lactitol, totally 4 kinds.When Fig. 2 represents the same maltitol that adds as sugar alcohol, change the response characteristics of sensor of the concentration of 4 kinds of maltitols.Wherein the interpolation concentration of sugar alcohol (as the concentration of reagent water solution) is to handle as existing sensors in 0 o'clock, is 5,10,25, is sensor of the present invention during 50mM.
Fig. 3 represents to use the above-mentioned sensor determination of making to change at the time dependent of crossing the background current of (30 ℃ of temperature, humidity exposes for 80% time) under the cruel environment.Use the Purified Water that does not contain glucose as test liquid.The variation of the by the time sensor response value of the whole blood that Fig. 4 represents to use concentration of glucose to be adjusted into 80mg/dL during as sample solution.In either case, mensuration all is respectively (0 hour) after the sensor production period, made back 6 hours, 12 hours, 24 hours, totally 4 points.
The amperometric determination condition is, confirms behind the filling sample solution, to promote enzyme reaction 25 seconds in cavity, measuring electrode and to electrode and detect the voltage that applies 0.2V between electrode, measuring the current value that obtains after 5 seconds afterwards.Detecting electrode herein, also uses as the part to electrode.
Measure frequency n and be n=10 period, map with its mean value among the figure in each concentration and mensuration.
As shown in Figure 1, interpolation is compared with not sugar alcohol contained existing sensor as the sensor response characteristics of the lactitol of sugar alcohol, is that high concentration region more than the 400mg/dL shows high response value tendency at concentration of glucose especially, can obtain the response characteristics of regression equation good (intercept is little, and slope is big).
As shown in Figure 2, identical when using maltitol with the situation of above-mentioned use lactitol as sugar alcohol, also can obtain good response characteristics.
By Fig. 3 and Fig. 4 as can be known, in the sensor that adds sugar alcohol, can effectively suppress the increase of the background current under the high humidity high temperature exposure environment, the response value that can obtain sensor through the time good storage stability with low uncertainty.
Prepare the blood-sugar level measuring sensor similarly to Example 1.But wherein replace sugar alcohol as suppressing the adjuvant that the background current time dependent rises with the sulfuric acid slaine, this sulfuric acid slaine is a magnesium sulphate.
Fig. 5 represents to use the above-mentioned sensor determination of making to change at the time dependent of crossing the background current of (30 ℃ of temperature, humidity exposes for 80% time) under the cruel environment.Use the Purified Water that does not contain glucose as test liquid.The variation of the by the time sensor response value of the whole blood that Fig. 6 represents to use concentration of glucose to be adjusted into 80mg/dL during as sample solution.
In either case, mensuration all is respectively (0 hour) after the sensor production period, made back 6 hours, 12 hours, 24 hours, totally 4 points.
Amperometric determination condition and mensuration number of times are with embodiment 1.
By Fig. 5 and Fig. 6 as can be known, the sugar alcohol that adds the sensor of sulfuric acid slaine and embodiment 1 is same, can effectively suppress the increase of the background current under the high humidity high temperature exposure environment, the response value that can realize sensor through the time good storage stability with low uncertainty.
On the insulated substrate of making by polyethylene terephthalate, utilize the serigraphy setting by the electrode layer that acts on the utmost point and the utmost point is formed, form thereon and contain enzyme (glucose oxidase), electron transit mediator (potassium ferricyanide), the reagent layer of hydrophilic macromolecule (carboxymethyl cellulose) and aliphatic carboxylic acid (concentration as reagent solution is 5mM), the dividing plate and the same cover plate that forms by polyethylene terephthalate of fitting afterwards and forming by polyethylene terephthalate, form as the cavity capillaceous that imports blood, make the blood-sugar level measuring sensor of 2 electrode modes.
Preparation is used aliphatic carboxylic acid malonic acid, glutaric acid, hexane diacid three kinds respectively as organic acid, and the existing sensor of not fatty family carboxylic acid, amounts to the sensor of 4 kind of 2 electrode mode.
Fig. 7 represents to use above-mentioned 4 kinds of sensor determinations making at the background current of crossing (40 ℃ of temperature, humidity exposes for 80% time) under the cruel environment, uses the Purified Water that does not contain glucose as test liquid.Mensuration all is respectively (0 day) after the sensor production period, made back 7 days, 14 days, 30 days, totally 4 points.The amperometric determination condition is, after sample solution (Purified Water) is filled in the cavity, promotes reaction 25 seconds, applies the voltage of 0.5V at the effect utmost point with to interpolar afterwards, measures the current value after 5 seconds.
Measuring number of times is n=10 all at each measuring point, maps with its mean value among Fig. 7.
As shown in Figure 7, the sensor that adds aliphatic carboxylic acid can suppress the rising of background current really, its escalating rate reduces according to the order of malonic acid, glutaric acid, hexane diacid, shows that molecular configuration is complicated more, straight chain is long more, molecular weight is big more, and the effect that suppresses the background current rising is big more.The current value that herein obtains is equivalent to the potassium ferricyanide amount that the reaction of the glucose oxidase and the potassium ferricyanide and carboxymethyl cellulose and the potassium ferricyanide generates.
Prepare biology sensor similarly to Example 3, estimate similarly to Example 3.Wherein use 3 kinds of the malic acid (butanedioic acid derivative) that the part of the hydrocarbon chain of carbocyclic ring carboxylic acid benzoic acid, phthalic acid and succinic acid replaced by hydroxyl as organic acid.
As shown in Figure 8, use any in benzoic acid, phthalic acid, the malic acid, can suppress the rising of background current similarly to Example 3.
On the insulated substrate of making by polyethylene terephthalate, utilize the serigraphy setting by the electrode layer that acts on the utmost point and the utmost point is formed, form thereon and contain enzyme (with the glucose dehydrogenase of pyrroloquinoline benzoquinones) as coenzyme, electron transit mediator (potassium ferricyanide), hydrophilic macromolecule (carboxymethyl cellulose) and aliphatic carboxylic acid (phthalic acid), amino acid whose reagent layer, the dividing plate and the same cover plate that forms by polyethylene terephthalate of fitting afterwards and forming by polyethylene terephthalate, form as the cavity capillaceous that imports blood, make the blood-sugar level measuring sensor of 2 electrode modes.
Preparation is used respectively in the molecule by at least one carboxyl and amino amino acid---glycocoll (Gly), serine (Ser), proline (Pro), threonine (Thr), lysine (Lys), methyl amimoacetic acid (derivant of glycocoll), taurine as organic acid; and do not contain amino acid whose existing sensor, amount to 8 kinds of sensors.
Use the sensor response characteristics when representing to use glucose in above-mentioned 8 kinds of sensor determination people whole bloods making as Fig. 9 and Figure 10.Concentration of glucose in the whole blood is respectively 40,80,350,600,700mg/dl.
The amperometric determination condition is, after sample solution (people's whole blood) is filled in the cavity, promotes reaction 25 seconds, applies the voltage of 0.5V at the effect utmost point with to interpolar afterwards, measures the current value that obtains after 5 seconds.
Measuring number of times is n=20 all at each measuring point, maps with its mean value among the figure.
By Fig. 9,10 as can be known, though because of the different response values of amino acid whose kind have some differences, but compare with not containing amino acid whose existing sensor, particularly the concentration of glucose is the above high concentration region of 480mg/dl, can confirm tremendous response value and linear raising.
Table 1 is the result that the deviation of the said n=20 sensor response value when measuring compares with the CV value.As shown in Table 1, add in the amino acid whose sensor of the present invention, can confirm the significantly optimization of CV value.This be because, in reagent layer, added the crystallization that amino acid has prevented the potassium ferricyanide, smoothly and in heterogeneity formed reagent layer, make the dissolubility of reagent and the diffusion homogeneous that becomes, alleviated and replied deviation.
Table 1
| Concentration | 40 | 80 | 350 | 600 | 700 |
| Existing sensor | 3.25％ | 2.48％ | 2.05％ | 2.11％ | 4.15％ |
| Gly-133mM | 2.15％ | 1.75％ | 1.55％ | 1.28％ | 1.05％ |
| Ser-95mM | 2.54％ | 2.11％ | 1.75％ | 1.45％ | 1.22％ |
| Pro-87mM | 2.38％ | 1.98％ | 1.69％ | 1.40％ | 1.18％ |
| Thr-84mM | 2.18％ | 2.00％ | 1.65％ | 1.39％ | 1.24％ |
| Lys-HCl-55mM | 2.48％ | 1.89％ | 1.58％ | 1.41％ | 1.14％ |
| Methyl amimoacetic acid-122mM | 2.65％ | 2.08％ | 1.68％ | 1.35％ | 1.25％ |
| Taurine | 2.18％ | 1.78％ | 1.43％ | 1.22％ | 1.10％ |
The foregoing description 1-5 has shown the biology sensor of measuring the concentration of glucose in the blood, form as sample solution, material and the biology sensor of determination object is not limited to these, for example, as the object sample solution can also be organism sample liquid such as saliva, interstitial cell fluid, urine or sweat except that blood, also can be Foods or drinks water etc.As the object material, except that glucose, can also use lactic acid, cholesterol, uric acid, ascorbic acid, cholerythrin etc.As galvanometric system, can be use in embodiment 1 and 2 by measure electrode, to electrode with detect the 3 electrode modes that electrode is formed, or use among the embodiment 3-5 only by measure electrode, to the 2 electrode modes that electrode is formed, any mode can obtain same result.Above-mentioned 3 electrode modes can be measured more accurately than 2 electrode modes.
Be that example has illustrated biology sensor in the present embodiment with the enzyme sensor, but the present invention is applicable to the material that utilizes beyond the enzyme too---as antibody, microorganism, DNA, RNA etc. as with test liquid in the biology sensor of molecular recognition elements of predetermined substance specific reaction.
Applicability on the industry
Biology sensor of the present invention, by in reagent layer, containing the combination that at least one carboxyl and amino organic acid or any one or they in the acylate are arranged in organic acid that at least one carboxyl is arranged in sugar alcohol, slaine, the molecule or acylate or the molecule, can not hinder thus enzyme reaction ground and suppress the by the time rising of background current, the various altogether unnecessary reactions between the miscellaneous material that exist in inhibition and the blood, can be fine and close and form in heterogeneity reagent layer, good stability and high performance biology sensor can be provided.
Claims (2)
1. biology sensor, its have the insulativity substrate, be provided with on the aforesaid substrate at least by the effect utmost point and electrode that the utmost point is formed and the reagent layer that contains enzyme and sugar alcohol at least that on above-mentioned electrode, forms, it is characterized in that said sugar alcohol is a kind of in maltitol, the lactitol or two kinds.
2. the biology sensor of claim 1 is characterized in that, contains electron transit mediator in this reagent layer.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000090362 | 2000-03-29 | ||
| JP90362/2000 | 2000-03-29 | ||
| JP90362/00 | 2000-03-29 | ||
| JP342537/2000 | 2000-11-09 | ||
| JP342537/00 | 2000-11-09 | ||
| JP2000342537 | 2000-11-09 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100586724A Division CN1268920C (en) | 2000-03-29 | 2001-03-28 | Biosensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1365446A CN1365446A (en) | 2002-08-21 |
| CN1187610C true CN1187610C (en) | 2005-02-02 |
Family
ID=26588660
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
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| CNB018007341A Expired - Lifetime CN1187610C (en) | 2000-03-29 | 2001-03-28 | Biosensor |
| CNB2004100586724A Expired - Lifetime CN1268920C (en) | 2000-03-29 | 2001-03-28 | Biosensor |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100586724A Expired - Lifetime CN1268920C (en) | 2000-03-29 | 2001-03-28 | Biosensor |
Country Status (4)
| Country | Link |
|---|---|
| US (4) | US6911131B2 (en) |
| EP (2) | EP2154522B1 (en) |
| CN (2) | CN1187610C (en) |
| WO (1) | WO2001073419A1 (en) |
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- 2001-03-28 CN CNB2004100586724A patent/CN1268920C/en not_active Expired - Lifetime
- 2001-03-28 EP EP09176735.0A patent/EP2154522B1/en not_active Expired - Lifetime
- 2001-03-28 US US09/979,842 patent/US6911131B2/en not_active Expired - Lifetime
- 2001-03-28 EP EP01921772.8A patent/EP1197749B1/en not_active Expired - Lifetime
- 2001-03-28 WO PCT/JP2001/002558 patent/WO2001073419A1/en active Application Filing
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| Publication number | Publication date |
|---|---|
| EP1197749A1 (en) | 2002-04-17 |
| WO2001073419A1 (en) | 2001-10-04 |
| CN1268920C (en) | 2006-08-09 |
| US20050194251A1 (en) | 2005-09-08 |
| US8673127B2 (en) | 2014-03-18 |
| EP2154522B1 (en) | 2017-03-01 |
| US20020179442A1 (en) | 2002-12-05 |
| US20100006432A1 (en) | 2010-01-14 |
| EP1197749B1 (en) | 2016-07-20 |
| EP2154522A2 (en) | 2010-02-17 |
| US7648617B2 (en) | 2010-01-19 |
| CN1590999A (en) | 2005-03-09 |
| US20110180404A1 (en) | 2011-07-28 |
| US6911131B2 (en) | 2005-06-28 |
| EP2154522A3 (en) | 2010-12-15 |
| CN1365446A (en) | 2002-08-21 |
| EP1197749A4 (en) | 2009-05-20 |
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